High-valent nonheme iron-oxo complexes: Synthesis, structure, and spectroscopy

被引:455
作者
McDonald, Aidan R.
Que, Lawrence, Jr. [1 ]
机构
[1] Univ Minnesota, Dept Chem, Minneapolis, MN 55455 USA
基金
美国国家科学基金会;
关键词
Bioinorganic chemistry; Dioxygen activation; Nonheme iron; Iron-oxo complexes; O-O BOND; ALPHA-KETOGLUTARATE DIOXYGENASE; SPIN OXOIRON(IV) COMPLEX; ISOPENICILLIN-N SYNTHASE; STEREOSPECIFIC ALKANE HYDROXYLATION; 2-HIS-1-CARBOXYLATE FACIAL TRIAD; ELECTRON-PARAMAGNETIC-RESONANCE; FE-2(MU-O)(2) DIAMOND CORE; DENSITY-FUNCTIONAL THEORY; FE-IV=O COMPLEXES;
D O I
10.1016/j.ccr.2012.08.002
中图分类号
O61 [无机化学];
学科分类号
070301 ; 081704 ;
摘要
High-valent iron-oxo intermediates have often been implicated, and in some cases identified, as the active oxidant in oxygen activating nonheme iron enzymes. Recent synthetic efforts have yielded pivotal insights into the generation of oxoiron(IV and V) complexes, and allowed thorough investigation of their spectroscopic, structural, and electronic properties. Furthermore, insight into the mechanisms by which nonheme iron sites activate dioxygen to yield high valent iron-oxo intermediates has been obtained. This review covers the great successes in iron-oxo chemistry over the past decade, detailing various efforts to obtain iron-oxo complexes in high yield, and to delve into their diverse structural and spectroscopic properties. (C) 2012 Elsevier B.V. All rights reserved.
引用
收藏
页码:414 / 428
页数:15
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